CN102408807B - High performance bionic antifouling composite paint and synthetic method thereof - Google Patents

Abstract

The invention specifically relates to a high performance bionic antifouling composite paint and a synthetic method thereof, belonging to the field of preparation of paints. The high performance bionic antifouling composite paint is characterized in that: the paint is prepared by mixing the component A of acrylic acid matrix resin, the component B of bionic functional matrix resin and auxiliary agents; the mass ratio of acrylic acid matrix resin to bionic functional matrix resin is 6-10: 1; the auxiliary agents comprise Fe2O3 and TiO3, wherein, the weight of Fe2O3 accounts for 2 to 4% of the total weight of the component A of acrylic acid matrix resin and the component B of bionic functional matrix resin, and the weight of TiO3 accounts for 1 to 2% of the total weight of the component A of acrylic acid matrix resin and the component B of bionic functional matrix resin. The high performance bionic antifouling composite paint has a surface capable of simulating the skin of sharks and has good effects of resisting pollution and reducing drag.

Description

High-performance biomimetic antifouling composite coating and its synthesis method

technical field

The invention belongs to the field of paint preparation, and in particular relates to a high-performance bionic antifouling composite paint and a synthesis method thereof.

Background technique

Marine biofouling of ship hulls is mainly plankton. Once plankton in the ocean approach the surface of the submerged hull with bacteria colonies attached, the following processes will occur: surface contact—surface sliding—finding a suitable position—secreting mucus to enhance attachment—series metamorphosis and attachment to the surface of the submerged object— Continuously multiply and grow. There are more than 2,000 species of fouling organisms in the world's oceans, and the common adherent organisms on the bottom of ships include barnacles, oysters, mussels, branch insects, sea squirts, green algae, brown algae, Enteromorpha, and polypia. Among them, barnacles, oysters, mussels, etc. grow rapidly after attaching to the bottom of the ship. During their growth process, they will generate a kind of tension, which can cut and destroy the paint film; at the same time, these organisms will also secrete organic acids, which will greatly accelerate the corrosion of the bottom steel plate and reduce the service life of the ship. Currently effective antifouling coatings for ship bottoms generally contain organic tin, etc., but these ingredients are harmful to marine ecology and are restricted by relevant national organizations. In addition, a large number of fouling organisms will increase the weight and navigation resistance of the ship, increase fuel consumption, and seriously affect the performance of the ship. Some data show that when the bottom of the ship is severely fouled, the marine bioaccumulation layer can be more than ten centimeters thick, and the weight per square meter can reach more than 20 kilograms, which will increase the weight of more than 200 tons for a ship with a bottom of nearly 10,000 square meters. . According to the docking situation of more than 1,500 ships, the British International Paint Company has calculated the following data: 5% of the ship's bottom fouling, the fuel consumption will increase by 10%; %, fuel consumption will increase by more than 40%. Statistics show that the annual economic loss of ocean-going vessels of more than 10,000 tons exceeds 1 million US dollars. Therefore, the research and application of high-performance ship antifouling materials not only has very important practical significance in reducing ship maintenance costs, reducing fuel costs, maintaining ship propulsion efficiency, suppressing carbon dioxide emissions, and protecting the earth's ecological environment. It also has high economic and social benefits.

Biomimetic antifouling paint is a new concept of antifouling. It starts from the biological adhesion mechanism and looks for antifouling polymer materials. For example, by imitating the state of the skin of some organisms, the coating is endowed with special surface properties, such as low surface energy, microphase separation, etc., so that marine organisms are not easy to attach or not firmly attached. Scientists in Germany have deeply studied the skin structure of sharks and dolphins, and simulated these surface structures by chemical means through bionic methods, and have made some progress. The material science research team of the University of Florida in the United States has developed an antifouling coating that is harmless to the marine environment based on the principle that sharks prevent marine organisms from adhering. Its surface is composed of numerous tiny diamond-shaped protrusions, the length of which is about 15 μm, and raised "ribs". The pattern composition can be clearly seen under the microscope. This kind of Gator Sharklet is called Gator Sharklet. In laboratory tests, it was found that the new coating has obvious antifouling and drag reduction effects, and at the same time can secrete mucus, making the epidermis very smooth and preventing the attachment of marine organisms. Japan's Kansai Paint Company and China Paint Company have also carried out related work. They use a coating with a microphase separation skin structure of a hydrophilic-hydrophobic substance as an antifouling material. The coating surface is uniformly swollen in seawater, and the simulation The behavior of dolphins secreting mucus when swimming can produce anti-fouling and drag-reducing effects, which can be described as a bionic anti-fouling coating in the true sense.

Contents of the invention

The technical problem to be solved by the present invention is to provide a high-performance bionic antifouling composite coating and a synthesis method thereof. The surface of the bionic antifouling composite coating can simulate shark skin and has a good antifouling and drag reduction effect.

In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is as follows:

A high-performance biomimetic antifouling composite coating is characterized in that it is formed by mixing A-component acrylic matrix resin, B-component biomimetic functional matrix resin and additives, and the mass ratio of the acrylic matrix resin to biomimetic functional matrix resin is 6 ~10:1, the additives are Fe ₂ O ₃ and TiO ₂ , by weight percentage, Fe ₂ O ₃ is 2% to 4% of the weight sum of A-component acrylic matrix resin and B-component biomimetic functional matrix resin %, _TiO2 is 1% to 2% of the weight sum of component A acrylic matrix resin and component B biomimetic functional matrix resin;

The acrylic base resin is composed of one of acrylic acid and methacrylic acid, one of ethyl acrylate and hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate, acrylic acid-β- Hydroxyethyl ester initiated polymerization obtained. In parts by weight, acrylic acid or methacrylic acid 10-50, ethyl acrylate or ethyl methacrylate 20-80, methyl methacrylate 20-80, butyl acrylate 50-100, β-hydroxyethyl acrylate 10-50, styrene 10-50;

The biomimetic functional matrix resin is obtained by adding sodium hydroxide to acrylic acid until 65-75% (percentage by weight) of the acrylic acid is neutralized into sodium acrylate, and then adding persimmon tannin with a mass concentration of 1-5g/L. Tannin solution is obtained by adding acrylamide, N,N'-methylenebisacrylamide and water-soluble inorganic peroxygen initiator, and reacting until viscous at 30-40°C. In parts by weight, acrylic acid 100 ～150, persimmon tannin solution 100～200, acrylamide 10～50.

According to the above scheme, the high-performance biomimetic antifouling composite coating also includes component C, and the amount of component C by weight is 1/10 to 1/6 of the total weight of component A and component B;

The C component is obtained by the following preparation method: add xylene and castor oil solvents to a reaction vessel previously passed through nitrogen to remove oxygen, gradually heat up to 50°C, and then add dibutyltin dilaurate and toluene dropwise while stirring -2,4-diisocyanate, obtained by raising the temperature to 80-90°C for 3-6 hours;

Among them: by weight, xylene 25, castor oil 40, dibutyltin dilaurate 0.02, toluene-2,4-diisocyanate 30.

According to the above scheme, the surface of the high-performance biomimetic antifouling composite paint forms micron-scale raised stripes similar to shark skin after the film is dried, and has a microphase separation structure.

The synthetic method of above-mentioned high-performance biomimetic antifouling composite coating is characterized in that: comprises the following steps:

(1) Preparation of component A: Add xylene and ethyl acetate solvents into the reaction vessel, then pass nitrogen to remove oxygen, gradually raise the temperature to 75-85°C, and add one of acrylic acid and methacrylic acid dropwise while stirring , one of ethyl acrylate and ethyl methacrylate, an oil-soluble organic initiator, a mixed solution of methyl methacrylate, butyl acrylate, β-hydroxyethyl acrylate and styrene, keep warm for more than 0.5h ;Add urea and zinc acetate solution dropwise to the above reaction solution, heat up to 150-160°C and reflux for 2-3 hours to obtain component A, set aside;

Among them: by weight, one of acrylic acid or methacrylic acid 10-50, one of ethyl acrylate or ethyl methacrylate 20-80, xylene 50-200, ethyl acetate 50-200, Methyl methacrylate 20-80, butyl acrylate 50-100, β-hydroxyethyl acrylate 10-50, styrene 10-50, oil-soluble organic initiator 0.01-1, urea 1-3, zinc acetate 1 ~3;

(2) Preparation of component B: in an ice-water bath, add sodium hydroxide to acrylic acid while stirring until 65-75% (weight percent) of acrylic acid is neutralized into sodium acrylate, and then add persimmon tannin mass Persimmon tannin solution with a concentration of 1-5g/L, then add acrylamide, N,N'-methylenebisacrylamide and water-soluble inorganic peroxygen initiator, react until viscous at 30-40°C, and set aside ;

Among them: by weight, acrylic acid 100-150, persimmon tannin solution 100-200, acrylamide 10-50, N,N'-methylenebisacrylamide 0.01-1, water-soluble inorganic peroxygen initiator 0.01 ~1;

(3) Mix components A and B at a mass ratio of 6 to 10:1, then add additives, mix evenly, and package for use.

According to the above scheme, the oil-soluble organic initiator is preferably benzoyl peroxide.

According to the above scheme, the water-soluble inorganic peroxygen initiator is preferably ammonium persulfate. Ammonium persulfate is preferred because of its low initiation temperature and accelerated decomposition under acidic conditions.

According to the above scheme, the persimmon tannin solution is obtained by crushing and pressing immature green persimmons to obtain persimmon juice, and then filtering the persimmon juice and storing it for more than half a year until the juice is reddish brown to obtain the mass concentration of persimmon tannin 1-5g/L, reserve.

According to the above scheme, the step (3) also includes: after mixing components A and B at a mass ratio of 6 to 10:1, adding component C, the amount of component C by weight is equal to component A and 1/10-1/6 of the total weight of component B, then add additives, mix evenly, and package for use;

The C component is obtained by the following preparation method: add xylene and castor oil solvents to a reaction vessel previously passed through nitrogen to remove oxygen, gradually heat up to 50°C, and then add dibutyltin dilaurate and toluene dropwise while stirring -2,4-diisocyanate, obtained by raising the temperature to 80-90°C for 3-6 hours, and set aside;

Among them: by weight, xylene 25, castor oil 40, dibutyltin dilaurate 0.02, toluene-2,4-diisocyanate 30.

Beneficial effects of the present invention: the nano-scale zinc oxide, added titanium dioxide and persimmon tannin reacted in the high-performance biomimetic antifouling composite coating provided by the present invention can prevent the growth of microorganisms such as bacteria when they are in contact with the water phase at the initial stage ; and water absorption swelling can make its surface form micron-scale regular concave-convex stripes similar to shark skin, and at the same time, the formation of part of the water-absorbing gel plays a bionic role of simulating shark skin's "shark engraving hydrocarbon" and secreting mucus, and the resulting "shark skin" The phenomenon of "carving hydrocarbons" can make marine attached organisms feel uncomfortable and make them not firmly attached. During the movement of the ship, the water flow can easily wash away the fouling organisms attached to the surface, and the resulting "shark hydrocarbons" structure can It plays a "ball bearing" effect during the ship's driving process, and produces a good anti-fouling and drag reduction effect. It is a kind of water-resistant and weather-resistant, high-strength, high-solid and low-viscosity, low-VOC emissions, non-toxic and environmentally friendly, energy-efficient A high-performance biomimetic antifouling composite material that can effectively reduce drag. It is especially suitable for related offshore installations such as offshore ships, surface ships, underwater submarines, piers of cross-sea bridges, and pillars of offshore oil drilling platforms.

Description of drawings

Fig. 1 is the distribution situation of the water-absorbing resin inside before the high-performance biomimetic antifouling composite coating of embodiment 1 absorbs water;

Fig. 2 is the distribution situation of the nano zinc oxide particles on the surface of the high-performance biomimetic antifouling composite paint of embodiment 1;

Fig. 3 and Fig. 4 are diagrams of the phenomenon of "shark engraving hydrocarbon" produced by the high-performance biomimetic antifouling composite coating in Example 1.

Detailed ways

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

Example 1:

1) Add 60 parts by weight of xylene and 60 parts by weight of ethyl acetate into the reaction kettle with jacket, condenser and constant pressure dropping funnel, pass nitrogen into the reaction kettle for 15-30 minutes, and then gradually raise the temperature to 75-85°C; Dissolve 0.2 parts by weight of benzoyl peroxide in 30 parts by weight of methyl methacrylate, 10 parts by weight of acrylic acid, 50 parts by weight of butyl acrylate, 20 parts by weight of β-hydroxyethyl acrylate, benzene 10 parts by weight of ethylene and 20 parts by weight of ethyl methacrylate in a monomer mixed solution, then added to the constant pressure dropping funnel, and the above solution was mixed for 1.5 hours under the condition that the stirring speed was more than 400 rpm. After the internal drop is completed, keep warm for half an hour; dissolve 2 parts by weight of urea and 2 parts by weight of zinc acetate in 20 parts by weight of water, drop them into the reactor, and heat up to 150-160°C for 2-3 hours Finally, take it out and use it as component A for later use;

2) Add 100 parts by weight of acrylic acid to a three-necked flask, then add 40 parts by weight of sodium hydroxide to neutralize the acrylic acid, and then add 140 parts by weight of persimmon tannin solution, which is made from immature green persimmons after grinding Crushed and squeezed to obtain persimmon juice, then filter the persimmon juice and seal it up for more than half a year until the juice turns reddish brown to obtain a persimmon tannin solution with a mass concentration of 1-5g/L, and finally add 12 parts by weight of acrylamide, 0.06 parts by weight of Ammonium sulfate and 0.06 parts by weight of N,N'-methylenebisacrylamide are heated to 30-40°C to react until viscous, taken out, and used as component B for later use;

3) Mix components A and B at a mass ratio of 10:1, add Fe ₂ O ₃ and TiO ₂ , Fe ₂ O ₃ is 3% of the weight sum of component A acrylic matrix resin and component B biomimetic functional matrix resin, TiO ₂ is 2% of the weight sum of the acrylic matrix resin of component A and the biomimetic functional matrix resin of component B. Mix evenly to obtain a brown viscous fluid that is a high-performance biomimetic antifouling composite coating, which is packaged for use.

Specific application method: first apply a primer on the surface to be painted, and then adjust the viscosity of the paint according to the needs, and then paint. The film can be applied as many times as needed.

The SEM test was carried out on the painted board to obtain the distribution of the water-absorbing resin and the distribution of nano-zinc oxide particles inside the high-performance biomimetic antifouling composite coating coated on the surface before absorbing water, as shown in Figure 1 and Figure 2 respectively; Brush the board for real sea and hang the board for half a year. It is observed that there are few stain points on the surface of the coating film, and the microbial adhesion is small, and the microbial adhesion is small. Combining Figures 3 and 4, it is shown that the high-performance biomimetic antifouling composite coating can prevent the growth of bacteria and other microorganisms when the high-performance biomimetic antifouling composite coating is in contact with the water phase at the initial stage; The "shark-carved hydrocarbon" phenomenon produced by the micro-phase separation structure can make marine attached organisms feel uncomfortable and make them not firmly attached. At the same time, the "shark-carved hydrocarbon" structure produced by it can produce a "ball bearing" effect during the ship's driving Play a very good role in antifouling and drag reduction.

Example 2:

1) Add 100 parts by weight of xylene and 200 parts by weight of ethyl acetate into a reaction kettle with a jacket, a condenser and a constant pressure dropping funnel, pass nitrogen into the reaction kettle for 15-30 minutes, and then gradually raise the temperature to 75 -85°C; Dissolve 0.09 parts by weight of benzoyl peroxide in 50 parts by weight of methyl methacrylate, 30 parts by weight of acrylic acid, 75 parts by weight of butyl acrylate, 10 parts by weight of β-hydroxyethyl acrylate, styrene After adding 30 parts by weight and 50 parts by weight of ethyl methacrylate into the monomer mixed solution, add it into the constant pressure dropping funnel, and under the condition that the stirring speed is more than 400 rpm, the above solution is mixed within 1.5 hours. After dripping, keep warm for half an hour; dissolve 2 parts by weight of urea and 2 parts by weight of zinc acetate in 20 parts by weight of water, drop them into the reactor, and heat up to 150-160°C for 2-3 hours Finally, take it out and use it as component A for later use;

2) Add 125 parts by weight of acrylic acid to a three-necked flask, then add 50 parts by weight of sodium hydroxide to neutralize the acrylic acid, and then add 100 parts by weight of persimmon tannin solution, which is made from immature green persimmons after grinding Crushed and squeezed to obtain persimmon juice, then filter the persimmon juice and seal it up for more than half a year until the juice is reddish brown to obtain a persimmon tannin solution with a mass concentration of 1-5g/L, and finally add 25 parts by weight of acrylamide, 0.02 parts by weight Ammonium persulfate and 0.02 parts by weight of N,N'-methylenebisacrylamide are heated to 30-40°C to react until viscous, taken out, and used as component B for later use;

3) Mix components A and B at a mass ratio of 8:1, add Fe ₂ O ₃ and TiO ₂ , Fe ₂ O ₃ is 2% of the weight sum of component A acrylic matrix resin and component B biomimetic functional matrix resin, _TiO2 is 1% of the weight sum of the acrylic matrix resin of component A and the biomimetic functional matrix resin of component B. Mix evenly to obtain a high-performance biomimetic antifouling composite coating, which is packaged for use.

Example 3:

1) Add 200 parts by weight of xylene and 100 parts by weight of ethyl acetate into a reaction kettle with a jacket, a condenser and a constant pressure dropping funnel, pass nitrogen into the reaction kettle for 15-30 minutes, and then gradually raise the temperature to 75 -85°C; 0.02 parts by weight of benzoyl peroxide was dissolved in 80 parts by weight of methyl methacrylate, 50 parts by weight of acrylic acid, 100 parts by weight of butyl acrylate, 50 parts by weight of β-hydroxyethyl acrylate, styrene After adding 50 parts by weight and 80 parts by weight of ethyl methacrylate into the monomer mixed solution, add it to the constant pressure dropping funnel, and under the condition of stirring, drop the above solution within 1.5 hours, and keep the temperature for half an hour. ; Dissolve 2 parts by weight of urea and 2 parts by weight of zinc acetate in 20 parts by weight of water, drop them into the reactor, heat up to 150-160°C and react for 2-3 hours, then take them out as component A spare;

2) Add 150 parts by weight of acrylic acid to a three-neck flask, then add 60 parts by weight of sodium hydroxide to neutralize the acrylic acid, and then add 200 parts by weight of persimmon tannin solution, which is made from immature green persimmons after grinding Crushed and squeezed to obtain persimmon juice, then filter the persimmon juice and seal it up for more than half a year until the juice is reddish brown to obtain a persimmon tannin solution with a mass concentration of 1-5g/L, and finally add 50 parts by weight of acrylamide, 0.9 parts by weight of Ammonium sulfate and 0.9 parts by weight of N,N'-methylenebisacrylamide are heated to 30-40°C to react until viscous, taken out, and used as component B for later use;

3) Mix components A and B at a mass ratio of 6:1, add Fe ₂ O ₃ and TiO ₂ , Fe ₂ O ₃ is 3% of the weight sum of component A acrylic matrix resin and component B biomimetic functional matrix resin, _TiO2 is 2% of the weight sum of the acrylic matrix resin of component A and the biomimetic functional matrix resin of component B, and then mixed evenly to obtain a high-performance biomimetic antifouling composite coating, which is packaged for use.

Example 4:

1) Add 60 parts by weight of xylene and 60 parts by weight of ethyl acetate into the reaction kettle with jacket, condenser and constant pressure dropping funnel, pass nitrogen into the reaction kettle for 15-30 minutes, then gradually raise the temperature to 75 -85°C; Dissolve 0.2 parts by weight of benzoyl peroxide in 30 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid, 50 parts by weight of butyl acrylate, 10 parts by weight of styrene, acrylic acid-β-hydroxy After 20 parts by weight of ethyl ester and 20 parts by weight of ethyl acrylate, they were added to the constant pressure dropping funnel, and the above solution was dripped within 1.5 hours under the condition that the stirring speed was above 400 rpm; Hours; take 20 parts by weight of water and just dissolve 2 parts by weight of urea and 2 parts by weight of zinc acetate, drop them into the reaction kettle, heat up to 150-160 ° C and react for 2-3 hours, take it out as component A spare;

2) Prepare component B according to the process steps of 2) in Example 1;

3) Mix components A and B in a mass ratio of 8:1, add Fe ₂ O ₃ and TiO ₂ , Fe ₂ O ₃ is 3% of the weight of component A acrylic matrix resin and component B biomimetic functional matrix resin %, TiO ₂ is 2% of the weight sum of the acrylic matrix resin of component A and the biomimetic functional matrix resin of component B, mixed evenly to obtain a high-performance biomimetic antifouling composite coating, which is packaged for use.

Example 5:

1) Prepare component A according to the process steps of step 1) in Example 1;

2) Prepare component B according to the process steps of step 2) in Example 1;

3) Add 25 parts by weight of xylene and 40 parts by weight of castor oil into a reaction kettle with a jacket, a condenser and a constant pressure dropping funnel, feed nitrogen into the reaction kettle for 15 to 30 minutes, and then gradually raise the temperature to 50°C; After adding 0.02 parts by weight of dibutyltin dilaurate to 30 parts by weight of toluene-2,4 diisocyanate, titrate it into the reactor within 0.5 hours under the condition that the stirring speed is above 400 rpm , then heat up to 80-90 ° C for 3 hours, take it out, and use it as component C for later use;

4) Mix A, B, and C in a weight ratio of 8:1:1.5, add Fe ₂ O ₃ and TiO ₂ , and Fe ₂ O ₃ is the acrylic matrix resin for component A and the biomimetic functional matrix resin for component B 3% of the weight sum, TiO ₂ is 2% of the weight sum of the acrylic matrix resin of the A component and the biomimetic functional matrix resin of the B component, and mix evenly to obtain a high-performance biomimetic antifouling composite coating.

Specific usage method: first apply a primer on the painted surface, then quickly apply the above-mentioned high-performance biomimetic antifouling composite coating on the primer, and air-dry at room temperature to form an antifouling film.

When the high-performance biomimetic antifouling materials prepared in the above examples are actually used, general thickeners, leveling agents, pigments, surfactants, matting agents, etc. can be added according to the properties of the coating itself during construction and in combination with construction needs.

Claims (7)

1. the bionical antifouling composite coating of high-performance, it is characterized in that: it is mixed by A part acrylic matrix resin, B component bionic function matrix resin and auxiliary agent, the mass ratio of described acrylic matrix resin and bionic function matrix resin is 6～10:1, and described auxiliary agent is Fe ₂O ₃And TiO ₂, by weight percentage, Fe ₂O ₃For A part acrylic matrix resin and B component bionic function matrix resin weight and 2%-4%, TiO ₂For A part acrylic matrix resin and B component bionic function matrix resin weight and 1%-2%;

Described A part acrylic matrix resin is to add dimethylbenzene and vinyl acetic monomer solvent in reaction vessel, letting nitrogen in and deoxidizing then, be warming up to 75-85 ℃ gradually, a kind of, oil soluble organic initiators in a kind of, ethyl propenoate in dropwise addition of acrylic acid and the methacrylic acid and the Jia Jibingxisuanyizhi, methyl methacrylate, butyl acrylate, senecioate-hydroxyl ethyl ester and cinnamic mixing solutions while stirring are more than the insulation reaction 0.5h; Urea and zinc acetate solution are added drop-wise in the above-mentioned reaction soln, are warmed up to and obtained in 150-160 ℃ of back flow reaction 2-3 hour;

Wherein: by weight, a kind of 10～50 in the acrylic or methacrylic acid, a kind of 20～80 in ethyl propenoate or the Jia Jibingxisuanyizhi, dimethylbenzene 50～200, vinyl acetic monomer 50～200, methyl methacrylate 20～80, butyl acrylate 50～100, senecioate-hydroxyl ethyl ester 10～50, vinylbenzene 10～50, oil soluble organic initiators 0.01～1, urea 1～3, zinc acetate 1～3;

Described B component bionic function matrix resin is that to add sodium hydroxide to weight percentage in vinylformic acid be that 65～75% vinylformic acid is neutralized to sodium acrylate, then to wherein adding the persimmon tannin solution that the persimmon tannin mass concentration is 1～5g/L, add acrylamide again, N, N '-methylene-bisacrylamide and water-soluble inorganic peroxide initiator, 30-40 ℃ of reaction is to thick obtaining, by weight, vinylformic acid 100～150, persimmon tannin solution 100～200, acrylamide 10～50, N, N '-methylene-bisacrylamide 0.01～1, water-soluble inorganic peroxide initiator 0.01～1.

2. the bionical antifouling composite coating of high-performance, it is characterized in that: it is made up of A part acrylic matrix resin, B component bionic function matrix resin, C component and auxiliary agent, the mass ratio of described acrylic matrix resin and bionic function matrix resin is 6～10:1, and described auxiliary agent is Fe ₂O ₃And TiO ₂, by weight percentage, Fe ₂O ₃For A part acrylic matrix resin and B component bionic function matrix resin weight and 2%-4%, TiO ₂For A part acrylic matrix resin and B component bionic function matrix resin weight and 1%-2%; The consumption of C component is 1/10～1/6 of A component and B component gross weight by weight;

Described A part acrylic matrix resin is to add dimethylbenzene and vinyl acetic monomer solvent in reaction vessel, letting nitrogen in and deoxidizing then, be warming up to 75-85 ℃ gradually, a kind of, oil soluble organic initiators in a kind of, ethyl propenoate in dropwise addition of acrylic acid and the methacrylic acid and the Jia Jibingxisuanyizhi, methyl methacrylate, butyl acrylate, senecioate-hydroxyl ethyl ester and cinnamic mixing solutions while stirring are more than the insulation reaction 0.5h; Urea and zinc acetate solution are added drop-wise in the above-mentioned reaction soln, are warmed up to and obtained in 150-160 ℃ of back flow reaction 2-3 hour;

Wherein: by weight, a kind of 10～50 in the acrylic or methacrylic acid, a kind of 20～80 in ethyl propenoate or the Jia Jibingxisuanyizhi, dimethylbenzene 50～200, vinyl acetic monomer 50～200, methyl methacrylate 20～80, butyl acrylate 50～100, senecioate-hydroxyl ethyl ester 10～50, vinylbenzene 10～50, oil soluble organic initiators 0.01～1, urea 1～3, zinc acetate 1～3;

Described B component bionic function matrix resin is that to add sodium hydroxide to weight percentage in vinylformic acid be that 65～75% vinylformic acid is neutralized to sodium acrylate, then to wherein adding the persimmon tannin solution that the persimmon tannin mass concentration is 1～5g/L, add acrylamide again, N, N '-methylene-bisacrylamide and water-soluble inorganic peroxide initiator, 30-40 ℃ of reaction is to thick obtaining, by weight, vinylformic acid 100～150, persimmon tannin solution 100～200, acrylamide 10～50, N, N '-methylene-bisacrylamide 0.01～1, water-soluble inorganic peroxide initiator 0.01～1;

Described C component adopts and is prepared as follows method and obtains: add dimethylbenzene and Viscotrol C solvent in the reaction vessel of letting nitrogen in and deoxidizing in advance, be warming up to 50 ℃ gradually, drip dibutyl tin laurate and Toluene-2,4-diisocyanate then while stirring, the 4-vulcabond is warming up to 80～90 ℃ of reaction 3-6h and getting;

Wherein: by weight, dimethylbenzene 25, Viscotrol C 40, dibutyl tin laurate 0.02, Toluene-2,4-diisocyanate, 4-vulcabond 30.

3. the bionical antifouling composite coating of high-performance according to claim 1 is characterized in that: the dry rear surface of the bionical antifouling composite coating film forming of described high-performance forms and is similar to the micron order convex stripe of shark skin, and is micro phase separation structure.

4. the synthetic method of the bionical antifouling composite coating of high-performance according to claim 1 is characterized in that: may further comprise the steps:

(1) preparation of A component: in reaction vessel, add dimethylbenzene and vinyl acetic monomer solvent, letting nitrogen in and deoxidizing then, be warming up to 75-85 ℃ gradually, a kind of, oil soluble organic initiators in a kind of, ethyl propenoate in dropwise addition of acrylic acid and the methacrylic acid and the Jia Jibingxisuanyizhi, methyl methacrylate, butyl acrylate, senecioate-hydroxyl ethyl ester and cinnamic mixing solutions while stirring are more than the insulation reaction 0.5h; Urea and zinc acetate solution are added drop-wise in the above-mentioned reaction soln, are warmed up to 150-160 ℃ of back flow reaction 2-3 hour, namely get the A component, standby;

Wherein: by weight, a kind of 10～50 in the acrylic or methacrylic acid, a kind of 20～80 in ethyl propenoate or the Jia Jibingxisuanyizhi, dimethylbenzene 50～200, vinyl acetic monomer 50～200, methyl methacrylate 20～80, butyl acrylate 50～100, senecioate-hydroxyl ethyl ester 10～50, vinylbenzene 10～50, oil soluble organic initiators 0.01～1, urea 1～3, zinc acetate 1～3;

(2) preparation of B component: in ice-water bath, the vinylformic acid that adds sodium hydroxide to weight percentage while stirring in the vinylformic acid and be 65-75% is neutralized to sodium acrylate, then to wherein adding the persimmon tannin solution that the persimmon tannin mass concentration is 1-5g/L, add acrylamide, N again, N '-methylene-bisacrylamide and water-soluble inorganic peroxide initiator, 30～40 ℃ of reactions are to thick, standby;

Wherein: by weight, vinylformic acid 100～150, persimmon tannin solution 100～200, acrylamide 10～50, N, N '-methylene-bisacrylamide 0.01～1, water-soluble inorganic peroxide initiator 0.01～1;

(3) A, B component are pressed mass ratio 6～10:1 and mix, add auxiliary agent then, mix, encapsulate stand-by.

5. the synthetic method of the bionical antifouling composite coating of high-performance according to claim 4, it is characterized in that: described oil soluble organic initiators is benzoyl peroxide.

6. the synthetic method of the bionical antifouling composite coating of high-performance according to claim 4, it is characterized in that: described water-soluble inorganic peroxide initiator is ammonium persulphate.

7. the synthetic method of the bionical antifouling composite coating of high-performance according to claim 4, it is characterized in that: described persimmon tannin solution is to obtain persimmon juice by immature not mature persimmon through pulverizing, squeeze to handle, seal up for safekeeping after then persimmon juice being filtered more than half a year and to be sorrel to juice and to make the persimmon tannin mass concentration and be 1-5g/L, standby.

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